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Properties of Solutions
Solutions
Solutions
• Solutions are homogeneous mixtures of two
or more pure substances.
• In a solution, the solute is dispersed uniformly
throughout the solvent.
Solutions
Solutions
The intermolecular
forces between solute
and solvent particles
must be strong enough
to compete with those
between solute particles
and those between
solvent particles.
Solutions
How Does a Solution Form?
As a solution forms, the solvent pulls solute
particles apart and surrounds, or solvates,
them.
Solutions
How Does a Solution Form
If an ionic salt is
soluble in water, it is
because the iondipole interactions
are strong enough
to overcome the
lattice energy of the
salt crystal.
Solutions
Energy Changes in Solution
• Simply put, three
processes affect the
energetics of the
process:
Separation of solute
particles
Separation of solvent
particles
New interactions
between solute and
solvent
Solutions
Energy Changes in Solution
The enthalpy
change of the
overall process
depends on H for
each of these steps.
Solutions
Why Do Endothermic
Processes Occur?
Things do not tend to
occur spontaneously
(i.e., without outside
intervention) unless
the energy of the
system is lowered.
Solutions
Why Do Endothermic
Processes Occur?
Yet we know that in
some processes,
like the dissolution
of NH4NO3 in water,
heat is absorbed,
not released.
Solutions
Enthalpy Is Only Part of the Picture
The reason is that
increasing the disorder
or randomness (known
as entropy) of a system
tends to lower the
energy of the system.
Solutions
Enthalpy Is Only Part of the Picture
So even though
enthalpy may increase,
the overall energy of
the system can still
decrease if the system
becomes more
disordered.
Solutions
Student, Beware!
Just because a substance disappears when it
comes in contact with a solvent, it doesn’t
mean the substance dissolved.
Solutions
Student, Beware!
• Dissolution is a physical change—you can get back the
original solute by evaporating the solvent.
• If you can’t, the substance didn’t dissolve, it reacted.
Solutions
Types of Solutions
• Saturated
Solvent holds as much
solute as is possible at
that temperature.
Dissolved solute is in
dynamic equilibrium
with solid solute
particles.
Solutions
Types of Solutions
• Unsaturated
Less than the
maximum amount of
solute for that
temperature is
dissolved in the
solvent.
Solutions
Types of Solutions
• Supersaturated
Solvent holds more solute than is normally
possible at that temperature.
These solutions are unstable; crystallization can
usually be stimulated by adding a “seed crystal” or
scratching the side of the flask.
Solutions
Factors Affecting Solubility
• Chemists use the axiom
“like dissolves like”:
Polar substances tend to
dissolve in polar solvents.
Nonpolar substances tend
to dissolve in nonpolar
solvents.
Solutions
Factors Affecting Solubility
The more similar the
intermolecular
attractions, the more
likely one substance
is to be soluble in
another.
Solutions
Factors Affecting Solubility
Glucose (which has
hydrogen bonding)
is very soluble in
water, while
cyclohexane (which
only has dispersion
forces) is not.
Solutions
Factors Affecting Solubility
• Vitamin A is soluble in nonpolar compounds
(like fats).
• Vitamin C is soluble in water.
Solutions
Gases in Solution
• In general, the
solubility of gases in
water increases with
increasing mass.
• Larger molecules
have stronger
dispersion forces.
Solutions
Gases in Solution
• The solubility of
liquids and solids
does not change
appreciably with
pressure.
• The solubility of a
gas in a liquid is
directly proportional
to its pressure.
Solutions
Henry’s Law
Sg = kPg
where
• Sg is the solubility of
the gas;
• k is the Henry’s law
constant for that gas in
that solvent;
• Pg is the partial
pressure of the gas
above the liquid.
Solutions
Temperature
Generally, the
solubility of solid
solutes in liquid
solvents increases
with increasing
temperature.
Solutions
Temperature
• The opposite is true
of gases:
Carbonated soft
drinks are more
“bubbly” if stored in
the refrigerator.
Warm lakes have
less O2 dissolved in
them than cool lakes.
Solutions
Ways of
Expressing
Concentrations
of Solutions
Solutions
Mass Percentage
mass of A in solution
100
Mass % of A =
total mass of solution
Solutions
Parts per Million and
Parts per Billion
Parts per Million (ppm)
mass of A in solution
106
ppm =
total mass of solution
Parts per Billion (ppb)
mass of A in solution
109
ppb =
total mass of solution
Solutions
Mole Fraction (X)
moles of A
XA =
total moles in solution
• In some applications, one needs the
mole fraction of solvent, not solute—
make sure you find the quantity you
need!
Solutions
Molarity (M)
M=
mol of solute
L of solution
• You will recall this concentration
measure from Chapter 4.
• Because volume is temperature
dependent, molarity can change with
temperature.
Solutions
Molality (m)
m=
mol of solute
kg of solvent
Because both moles and mass do not
change with temperature, molality
(unlike molarity) is not temperature
dependent.
Solutions
Changing Molarity to Molality
If we know the
density of the
solution, we can
calculate the
molality from the
molarity, and vice
versa.
Solutions
Colligative Properties
• Changes in colligative properties
depend only on the number of solute
particles present, not on the identity of
the solute particles.
• Among colligative properties are
Vapor pressure lowering
Boiling point elevation
Melting point depression
Osmotic pressure
Solutions
Vapor Pressure
Because of solutesolvent intermolecular
attraction, higher
concentrations of
nonvolatile solutes
make it harder for
solvent to escape to
the vapor phase.
Solutions
Vapor Pressure
Therefore, the vapor
pressure of a solution
is lower than that of
the pure solvent.
Solutions
Raoult’s Law
PA = XAPA
where
• XA is the mole fraction of compound A
• PA is the normal vapor pressure of A at
that temperature
NOTE: This is one of those times when you
want to make sure you have the vapor
pressure of the solvent.
Solutions
Boiling Point Elevation and
Freezing Point Depression
Nonvolatile solutesolvent interactions
also cause solutions
to have higher boiling
points and lower
freezing points than
the pure solvent.
Solutions
Boiling Point Elevation
The change in boiling
point is proportional to
the molality of the
solution:
Tb = Kb m
Tb is added to the normal
boiling point of the solvent.
where Kb is the molal
boiling point elevation
constant, a property of
the solvent.
Solutions
Freezing Point Depression
• The change in freezing
point can be found
similarly:
Tf = Kf m
Tf is subtracted from the normal
freezing point of the solvent.
• Here Kf is the molal
freezing point
depression constant of
the solvent.
Solutions
Boiling Point Elevation and
Freezing Point Depression
Note that in both
equations, T does
not depend on what
the solute is, but
only on how many
particles are
dissolved.
Tb = Kb m
Tf = Kf m
Solutions
Colligative Properties of
Electrolytes
Since these properties depend on the number of
particles dissolved, solutions of electrolytes (which
dissociate in solution) should show greater changes
than those of nonelectrolytes.
Solutions
Colligative Properties of
Electrolytes
However, a 1 M solution of NaCl does not show
twice the change in freezing point that a 1 M
solution of methanol does.
Solutions
van’t Hoff Factor
One mole of NaCl in
water does not
really give rise to
two moles of ions.
Solutions
van’t Hoff Factor
Some Na+ and Cl−
reassociate for a
short time, so the
true concentration of
particles is
somewhat less than
two times the
concentration of
NaCl.
Solutions
The van’t Hoff Factor
• Reassociation is
more likely at higher
concentration.
• Therefore, the
number of particles
present is
concentration
dependent.
Solutions
The van’t Hoff Factor
We modify the
previous equations
by multiplying by the
van’t Hoff factor, i
Tf = Kf m i
Solutions
Osmosis
• Some substances form semipermeable
membranes, allowing some smaller
particles to pass through, but blocking
other larger particles.
• In biological systems, most
semipermeable membranes allow water
to pass through, but solutes are not free
to do so.
Solutions
Osmosis
In osmosis, there is net movement of solvent from
the area of higher solvent concentration (lower
solute concentration) to the are of lower solvent
concentration (higher solute concentration).
Solutions
Osmotic Pressure
• The pressure required to stop osmosis,
known as osmotic pressure, , is
=(
n
)
RT = MRT
V
where M is the molarity of the solution
If the osmotic pressure is the same on both sides
of a membrane (i.e., the concentrations are the
same), the solutions are isotonic.
Solutions
Osmosis in Blood Cells
• If the solute
concentration outside
the cell is greater than
that inside the cell, the
solution is hypertonic.
• Water will flow out of
the cell, and crenation
results.
Solutions
Osmosis in Cells
• If the solute
concentration outside
the cell is less than
that inside the cell, the
solution is hypotonic.
• Water will flow into the
cell, and hemolysis
results.
Solutions
Molar Mass from
Colligative Properties
We can use the
effects of a colligative
property such as
osmotic pressure to
determine the molar
mass of a compound.
Solutions
Colloids:
Suspensions of particles larger than
individual ions or molecules, but too small to
be settled out by gravity.
Solutions
Tyndall Effect
• Colloidal suspensions
can scatter rays of light.
• This phenomenon is
known as the Tyndall
effect.
Solutions
Colloids in Biological Systems
Some molecules have
a polar, hydrophilic
(water-loving) end and
a nonpolar,
hydrophobic (waterhating) end.
Solutions
Colloids in Biological Systems
Sodium stearate
is one example
of such a
molecule.
Solutions
Colloids in Biological Systems
These molecules
can aid in the
emulsification of fats
and oils in aqueous
solutions.
Solutions
Solutions
Solutions
• Solutions are homogeneous mixtures of two
or more pure substances.
• In a solution, the solute is dispersed uniformly
throughout the solvent.
Solutions
Solutions
The intermolecular
forces between solute
and solvent particles
must be strong enough
to compete with those
between solute particles
and those between
solvent particles.
Solutions
How Does a Solution Form?
As a solution forms, the solvent pulls solute
particles apart and surrounds, or solvates,
them.
Solutions
How Does a Solution Form
If an ionic salt is
soluble in water, it is
because the iondipole interactions
are strong enough
to overcome the
lattice energy of the
salt crystal.
Solutions
Energy Changes in Solution
• Simply put, three
processes affect the
energetics of the
process:
Separation of solute
particles
Separation of solvent
particles
New interactions
between solute and
solvent
Solutions
Energy Changes in Solution
The enthalpy
change of the
overall process
depends on H for
each of these steps.
Solutions
Why Do Endothermic
Processes Occur?
Things do not tend to
occur spontaneously
(i.e., without outside
intervention) unless
the energy of the
system is lowered.
Solutions
Why Do Endothermic
Processes Occur?
Yet we know that in
some processes,
like the dissolution
of NH4NO3 in water,
heat is absorbed,
not released.
Solutions
Enthalpy Is Only Part of the Picture
The reason is that
increasing the disorder
or randomness (known
as entropy) of a system
tends to lower the
energy of the system.
Solutions
Enthalpy Is Only Part of the Picture
So even though
enthalpy may increase,
the overall energy of
the system can still
decrease if the system
becomes more
disordered.
Solutions
Student, Beware!
Just because a substance disappears when it
comes in contact with a solvent, it doesn’t
mean the substance dissolved.
Solutions
Student, Beware!
• Dissolution is a physical change—you can get back the
original solute by evaporating the solvent.
• If you can’t, the substance didn’t dissolve, it reacted.
Solutions
Types of Solutions
• Saturated
Solvent holds as much
solute as is possible at
that temperature.
Dissolved solute is in
dynamic equilibrium
with solid solute
particles.
Solutions
Types of Solutions
• Unsaturated
Less than the
maximum amount of
solute for that
temperature is
dissolved in the
solvent.
Solutions
Types of Solutions
• Supersaturated
Solvent holds more solute than is normally
possible at that temperature.
These solutions are unstable; crystallization can
usually be stimulated by adding a “seed crystal” or
scratching the side of the flask.
Solutions
Factors Affecting Solubility
• Chemists use the axiom
“like dissolves like”:
Polar substances tend to
dissolve in polar solvents.
Nonpolar substances tend
to dissolve in nonpolar
solvents.
Solutions
Factors Affecting Solubility
The more similar the
intermolecular
attractions, the more
likely one substance
is to be soluble in
another.
Solutions
Factors Affecting Solubility
Glucose (which has
hydrogen bonding)
is very soluble in
water, while
cyclohexane (which
only has dispersion
forces) is not.
Solutions
Factors Affecting Solubility
• Vitamin A is soluble in nonpolar compounds
(like fats).
• Vitamin C is soluble in water.
Solutions
Gases in Solution
• In general, the
solubility of gases in
water increases with
increasing mass.
• Larger molecules
have stronger
dispersion forces.
Solutions
Gases in Solution
• The solubility of
liquids and solids
does not change
appreciably with
pressure.
• The solubility of a
gas in a liquid is
directly proportional
to its pressure.
Solutions
Henry’s Law
Sg = kPg
where
• Sg is the solubility of
the gas;
• k is the Henry’s law
constant for that gas in
that solvent;
• Pg is the partial
pressure of the gas
above the liquid.
Solutions
Temperature
Generally, the
solubility of solid
solutes in liquid
solvents increases
with increasing
temperature.
Solutions
Temperature
• The opposite is true
of gases:
Carbonated soft
drinks are more
“bubbly” if stored in
the refrigerator.
Warm lakes have
less O2 dissolved in
them than cool lakes.
Solutions
Ways of
Expressing
Concentrations
of Solutions
Solutions
Mass Percentage
mass of A in solution
100
Mass % of A =
total mass of solution
Solutions
Parts per Million and
Parts per Billion
Parts per Million (ppm)
mass of A in solution
106
ppm =
total mass of solution
Parts per Billion (ppb)
mass of A in solution
109
ppb =
total mass of solution
Solutions
Mole Fraction (X)
moles of A
XA =
total moles in solution
• In some applications, one needs the
mole fraction of solvent, not solute—
make sure you find the quantity you
need!
Solutions
Molarity (M)
M=
mol of solute
L of solution
• You will recall this concentration
measure from Chapter 4.
• Because volume is temperature
dependent, molarity can change with
temperature.
Solutions
Molality (m)
m=
mol of solute
kg of solvent
Because both moles and mass do not
change with temperature, molality
(unlike molarity) is not temperature
dependent.
Solutions
Changing Molarity to Molality
If we know the
density of the
solution, we can
calculate the
molality from the
molarity, and vice
versa.
Solutions
Colligative Properties
• Changes in colligative properties
depend only on the number of solute
particles present, not on the identity of
the solute particles.
• Among colligative properties are
Vapor pressure lowering
Boiling point elevation
Melting point depression
Osmotic pressure
Solutions
Vapor Pressure
Because of solutesolvent intermolecular
attraction, higher
concentrations of
nonvolatile solutes
make it harder for
solvent to escape to
the vapor phase.
Solutions
Vapor Pressure
Therefore, the vapor
pressure of a solution
is lower than that of
the pure solvent.
Solutions
Raoult’s Law
PA = XAPA
where
• XA is the mole fraction of compound A
• PA is the normal vapor pressure of A at
that temperature
NOTE: This is one of those times when you
want to make sure you have the vapor
pressure of the solvent.
Solutions
Boiling Point Elevation and
Freezing Point Depression
Nonvolatile solutesolvent interactions
also cause solutions
to have higher boiling
points and lower
freezing points than
the pure solvent.
Solutions
Boiling Point Elevation
The change in boiling
point is proportional to
the molality of the
solution:
Tb = Kb m
Tb is added to the normal
boiling point of the solvent.
where Kb is the molal
boiling point elevation
constant, a property of
the solvent.
Solutions
Freezing Point Depression
• The change in freezing
point can be found
similarly:
Tf = Kf m
Tf is subtracted from the normal
freezing point of the solvent.
• Here Kf is the molal
freezing point
depression constant of
the solvent.
Solutions
Boiling Point Elevation and
Freezing Point Depression
Note that in both
equations, T does
not depend on what
the solute is, but
only on how many
particles are
dissolved.
Tb = Kb m
Tf = Kf m
Solutions
Colligative Properties of
Electrolytes
Since these properties depend on the number of
particles dissolved, solutions of electrolytes (which
dissociate in solution) should show greater changes
than those of nonelectrolytes.
Solutions
Colligative Properties of
Electrolytes
However, a 1 M solution of NaCl does not show
twice the change in freezing point that a 1 M
solution of methanol does.
Solutions
van’t Hoff Factor
One mole of NaCl in
water does not
really give rise to
two moles of ions.
Solutions
van’t Hoff Factor
Some Na+ and Cl−
reassociate for a
short time, so the
true concentration of
particles is
somewhat less than
two times the
concentration of
NaCl.
Solutions
The van’t Hoff Factor
• Reassociation is
more likely at higher
concentration.
• Therefore, the
number of particles
present is
concentration
dependent.
Solutions
The van’t Hoff Factor
We modify the
previous equations
by multiplying by the
van’t Hoff factor, i
Tf = Kf m i
Solutions
Osmosis
• Some substances form semipermeable
membranes, allowing some smaller
particles to pass through, but blocking
other larger particles.
• In biological systems, most
semipermeable membranes allow water
to pass through, but solutes are not free
to do so.
Solutions
Osmosis
In osmosis, there is net movement of solvent from
the area of higher solvent concentration (lower
solute concentration) to the are of lower solvent
concentration (higher solute concentration).
Solutions
Osmotic Pressure
• The pressure required to stop osmosis,
known as osmotic pressure, , is
=(
n
)
RT = MRT
V
where M is the molarity of the solution
If the osmotic pressure is the same on both sides
of a membrane (i.e., the concentrations are the
same), the solutions are isotonic.
Solutions
Osmosis in Blood Cells
• If the solute
concentration outside
the cell is greater than
that inside the cell, the
solution is hypertonic.
• Water will flow out of
the cell, and crenation
results.
Solutions
Osmosis in Cells
• If the solute
concentration outside
the cell is less than
that inside the cell, the
solution is hypotonic.
• Water will flow into the
cell, and hemolysis
results.
Solutions
Molar Mass from
Colligative Properties
We can use the
effects of a colligative
property such as
osmotic pressure to
determine the molar
mass of a compound.
Solutions
Colloids:
Suspensions of particles larger than
individual ions or molecules, but too small to
be settled out by gravity.
Solutions
Tyndall Effect
• Colloidal suspensions
can scatter rays of light.
• This phenomenon is
known as the Tyndall
effect.
Solutions
Colloids in Biological Systems
Some molecules have
a polar, hydrophilic
(water-loving) end and
a nonpolar,
hydrophobic (waterhating) end.
Solutions
Colloids in Biological Systems
Sodium stearate
is one example
of such a
molecule.
Solutions
Colloids in Biological Systems
These molecules
can aid in the
emulsification of fats
and oils in aqueous
solutions.
Solutions